This application is a 371 of PCT/JP01/05037, filed Jun. 13, 2001.
1. Technical Field
The present invention relates to amide compounds and their use for fungicide.
2. Background Arts
The present invention provides an amide compound which can be more excellent fungicidal active ingredient, though various fungicides for controlling plant diseases have been known hitherto.
The present invention provides an amide compound given by formula [I]: 
wherein R1 represents a C1-C10 haloalkyl group, C2-C10 haloalkenyl group, C3-C10 haloalkynyl group, C3-C8 halocycloalkyl group or C3-C10 alkynyl group; R2 represents a hydrogen atom or C1-C3 alkyl group (namely, methy, ethyl, propyl and isopropyl); X represents an oxygen atom or sulfur atom; Y represents an oxygen atom or sulfur atom; Ar represents an aromatic group; A represents an ethylene group or trimethylene group, said ethylene group and trimethylene group may be substituted by one or more selected from halogen atom, amino group, hydroxy group, cyano group, nitro group, C1-C6 alkyl group, C3-C6 cycloalkyl group, C3-C6 cycloalkenyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group, C1-C6 haloalkylthio group, C2-C6 (alkoxycarbonyl) group and tri(C1-C6 alkyl)silyl group; Z1 and Z2 are the same or different and represents a halogen atom (chlorine, bromine, fluorine, iodine), C1-C6 alkyl group, C1-C6 haloalkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, C3-C6 cycloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C2-C6 (alkoxyalkoxy) group, C4-C6 (cycloalkylalkoxy) group, C3-C6 alkenyloxy group, C3-C6 haloalkenyloxy group, C3-C6 alkynyloxy group, C3-C6 haloalkynyloxy group, C3-C6 cycloalkoxy group, C3-C6 cycloalkenyloxy group, cyano C1-C5 alkoxy group, C1-C6 alkylthio group, C1-C6 haloalkylthio group (C1-C5 alkoxy)carbonyl group, phenoxy group, benzyloxy group, hydroxy group or cyano group, the benzene ring of said phenyl group and benzyloxy group may be substituted by one or more selected from halogen atom (chlorine, bromine, fluorine, iodine) C1-C6 alkyl group, C1-C6 alkoxy group, trifluoromethyl group, amino group and nitro group; and Z1 and Z2 may represents C2-C6 alkylenedioxy group together, (hereinafter, referred to as the present compound) and fungicide comprising it as an active ingredient.
In the present invention, examples of the C1-C10 haloalkyl group for R1 include fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, chlorofluoromethyl, bromodifluoromethyl, trichloromethyl, dichlorobromomethyl, 1,1,2,2,2-pentafluoroethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl and 2-fluoroethyl; examples of the C2-C10 haloalkenyl group include 2-fluorovinyl, 2,2-difluorovinul, trifluorovinyl, 3-chloropropenyl, 3,3-dichloropropenyl, 3-fluoropropenyl, 3,3-difluoropropenyl, 2,3,3-trifluoropropenyl and 10-fluoro-2-decenyl; examples of the C3-C10 haloalkynyl group include 3-fluoro-2-propynyl, 3-chloro-2-propynyl, 3-bromo-2-propynyl, 3-iodo-2-propynyl, 4-fluoro-2-butynyl, 4,4-difluoro-2-butynyl, 4,4,4-trifluoro-2-butynyl and 4-chloro-2-butynyl; examples of the C3-C8 halocycloalkyl group include 2,2-difluorocyclopropyl, 2,3,4-trifluorocyclobutyl, 2,5-dichlorocyclopentyl, 4,4-difluorocyclohexy and 2-chlorocycloheptyl; and examples of the C3-C10 alkynyl group include 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 5-pentynyl and 7-octynyl. Among them, C1-C3 haloalkyl group, C2-C3 haloalkenyl group, C3-C5-haloalkynyl group, C3-C6 halocycloalkyl group and C3-C8 alkynyl group are preferable, and especialy fluoromethyl, difluoromethyl, trifluoromethyl and 2-propynyl are more preferable for R1.
In the present invention, examples of the aromatic group for Ar include aromatic hydrocarbyl groups such as phenyl, naphthyl (1-naphthyl, 2-naphthyl) and so on; and aromatic heterocyclic groups such as thienyl (2-thienyl, 3-thienyl), furyl (2-furyl, 3-furyl), pyrrolyl (1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), pyrazolyl (1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (1-imidazolyl, 2-imidazolyl, 4-imidazolyl), triazolyl (1-triazolyl, 4-triazolyl), tetrazolyl (1-tetrazolyl, 5-tetrazolyl), thiazolyl (2-thiazolyl, 4-thiazolyl, 5-thiazolyl), isothiazolyl (3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl), oxazolyl (2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isoxazolyl (3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), thiadiazolyl (e.g. 1,2,5-thiadiazol-4-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-thiadiazol-5-yl), pyridyl (2-pyridyl, 3-pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl, pyridazinyl (3-pyridazinyl, 4-pyridazinyl), benzofuryl (2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, 7-benzofuryl), benzothienyl (2-benzothienyl, 3-benzothienyl, 4-benzothienyl, 5-benzothienyl, 6-benzothienyl, 7-benzothienyl), indolyl (1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzothiazolyl (2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), benzimidazolyl (1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl), benzopyrazolyl (1-benzopyrazolyl, 2-benzopyrazolyl, 3-benzopyrazolyl, 4-benzopyrazolyl, 5-benzopyrazolyl, 6-benzopyrazolyl, 7-benzopyrazolyl), quinolyl (2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl), isoquinolyl (1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl), pyrazolopyrimidinyl, imidazopyrimidinyl, thiophenopyrimidinyl, thiazolopyrimidinyl, pyrazolopyridyl, imidazopyridyl, thiophenopyridyl, thiazolopyridyl and so on; and said aromatic hydrocarbyl group and aromatic heterocyclic group may be substituted. Typical examples of the substituents include halogen (chlorine, bromine, fluorine, iodine), amino, hydroxy, cyano, nitro, C1-C10 alkyl (e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1-methylpropyl, pentyl, 1-methylbutyl, 1-ethylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,2-dimethylbutyl, 1,1-dimethylpropyl, hexyl, 1-methylpentyl, 1-ethylpentyl, 3,3-dimethylbutyl, heptyl, 3,7-dimethyloctyl), C1-C10 haloalkyl (e.g. trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl), cyano C1-C9 alkyl (e.g. cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 3-cyanopropyl, 5-cyanohexyl), C2-C10 alkenyl (e.g. vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3,3-dimethyl-1-butenyl, 4-pentenyl, 5-hexenyl), C2-C10 haloalkenyl (e.g. 2-fluorovinyl, 3-chloro-2-propenyl, 3,3-dichloro-2-propenyl, 2-fluoro-1-propenyl, 3,3,3-trifluoro-1-propenyl, 4-chloro-3-butenyl, 2-chloro-3-methyl-1-butenyl, 2-fluoro-5-hexenyl), C2-C10 alkynyl (e.g. ethynyl, 1-propynyl, 2-propynyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 1-butynyl, 3,3-dimethyl-1-butynyl, 3-butynyl, 4-pentynyl, 5-hexynyl), C2-C10 haloalkynyl (e.g. 2-fluoroethynyl, 2-chloroethynyl, 3-chloro-2-propynyl, 4-fluoro-3-butynyl, 5-chloro-4-pentynyl, 6-bromo-5-hexynyl), C3-C6 cycloalkyl (e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), C3-C6 cycloalkenyl (e.g. 2-cyclopentenyl, 2-cyclohexenyl), C1-C10 alkoxy (e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, pentyloxy), C1-C10 haloalkoxy (e.g. trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, chlorodifluoromethoxy, fluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy), C3-C10 alkenyloxy (e.g. 2-propenyloxy, 1-methyl-2-propenyloxy, 1-ethyl-2-propenyloxy, 2-butenyloxy, 3-butenyloxy, 2,2-dimethyl-3-butenyloxy, 4-pentenyloxy, 5-hexenyloxy), C3-C10 haloalkenyloxy (e.g. 3-chloro-2-propenyloxy, 3,3-dichloro-2-propenyloxy, 2-fluoro-1-propenyloxy, 3,3,3-trifluoro-1-propenyloxy, 4-chloro-3-butenyloxy, 2-chloro-3-methyl-1-butenyloxy, 2-fluoro-5-hexenyloxy), C3-C10 alkynyloxy (e.g. 2-propynyloxy, 1-methyl-2-propynyloxy, 1-ethyl-2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 4-pentynyloxy, 5-hexynyloxy), C3-C10 haloalkynyloxy (e.g. 3-chloro-2-propynyloxy, 3-fluoro-2-propynyloxy, 4-fluoro-3-butynyloxy, 5-chloro-4-pentynyloxy, 6-bromo-5-hexynyloxy), C3-C10 cycloalkoxy (e.g. cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclooctyloxy), cyano C1-C9 alkoxy (e.g. cyanomethoxy, 1-cyanoethoxy, 2-cyanoethoxy, 3-cyanopropoxy, 5-cyanohexyloxy), C1-C10 alkylthio (e.g. methylthio, ethylthio, propylthio, butylthio, isobutylthio, sec-butylthio, pentylthio, hexylthio), C1-C10 haloalkylthio (e.g. trifluoromethylthio, difluoromethylthio, bromodifluoromethylthio, chlorodifluoromethylthio, fluoromethylthio, 2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio), C2-C10 (alkoxycarbonyl) (e.g. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl), tri(C1-C6 alkyl)silyl (e.g. trimethylsilyl, triethylsilyl), C3-C5 alkylene (e.g. trimethylene, tetramethylene, pentamethylene) and methylenedioxy. Among them, preferred Ar""s are 4-methylphenyl group, 4-ethylphenyl group, 4-methoxyphenyl group, 4-chlorophenyl group, 4-trifluoromethylphenyl group, 3,4-tetramethylenephenyl group (5,6,7,8-tetrahydronaphthalen-2-yl group), 3,4-trimethylenephenyl group (indan-5-yl group) and 2-naphthyl group.
In the present invention, the ethylene group (xe2x80x94CH2CH2xe2x80x94) and trimethylene group for A may be substituted by at least one selected from halogen (chlorine, bromine, fluorine, iodine), amino, hydroxy, cyano, nitro, C1-C6 alkyl (e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl), C3-C6 cycloalkyl (e.g. cyclopropyl, cyclopentyl, cyclohexyl), C3-C6 cycloalkenyl, C1-C6 alkoxy (e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, pentyloxy), C1-C6 haloalkoxy (e.g. trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, chlorodifluoromethoxy, fluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy), C1-C6 alkylthio (e.g. methylthio, ethylthio, propylthio, butylthio, isobutylthio, sec-butylthio, pentylthio, hexylthio), C1-C6 haloalkylthio (e.g. trifluoromethylthio, difluoromethylthio, bromodifluoromethylthio, chlorodifluoromethylthio, fluoromethylthio, 2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio), C2-C6 (alkoxycarbonyl) (e.g. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl) and (C1-C6 alkyl)silyl (e.g. trimethylsilyl, triethylsilyl). Among them, ethylene (xe2x80x94CH2CH2xe2x80x94) is preferable for A.
In the present invention, examples of the C1-C6 alkyl group for Z1 and Z2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, 1-methylbutyl, 1-ethylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, hexyl, 1-methylpentyl and 3,3-dimethylbutyl; examples of the C1-C6 haloalkyl group include trifluoromethyl, 2,2,2-trifluoroethyl and 1,1,2,2-tetrafluoroethyl; examples of the C2-C6 alkenyl group include vinyl, 2-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 4-methyl-3-butenyl, 4-pentenyl and 5-hexenyl; C2-C6 alkynyl group include ethynyl, 2-propynyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-butynyl, 2-pentynyl and 4,4-dimethyl-2-pentynyl; examples of the C3-C6 cycloalkyl group include cyclopropyl, cyclopentyl and cyclohexyl; examples of the C1-C6 alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and pentyloxy; examples of the C1-C6 haloalkoxy group include trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, chlorodifluoromethoxy, fluoromethoxy, 2,2,2-trifluoroethoxy and 1,1,2,2-tetrafluoroethoxy; examples of the C2-C6 (alkoxyalkoxy) group include methoxymethoxy, 2-methoxyethoxy, ethoxymethoxy and isopropoxymethoxy; examples of the C4-C6 (cycloalkylalkoxy) group include cyclopropylmethyl; examples of the C3-C6 alkenyloxy group include 2-propenyloxy, 1-methyl-2-propenyloxy, 2-methyl-2-propenyloxy, 2-butenyloxy, 3-butenyloxy, 3-methyl-2-butenyloxy, 4-methyl-3-butenyloxy, 4-pentenyloxy and 5-hexenyloxy; examples of the C3-C6 haloalkenyloxy group include 2-chloro-2-propenyloxy, 3-fluoro-2-propenyloxy, 3-chloro-2-propenyloxy, 3-bromo-2-propenyloxy, 3,3-dichloro-2-propenyloxy, 2,3, 3-trifluoro-2-propenyloxy, 4-chloro-2-butenyloxy, 4-chloro-3-butenyloxy and 3-chloro-3-butenyloxy; examples of the C3-C6 alkynyloxy group include 2-propynyloxy, 1-methyl-2-propynyloxy, 1-ethyl-2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl-2-butynyloxy, 2-pentynyloxy, 4-pentynyloxy and 4,4-dimethyl-2-pentynyloxy; examples of the C3-C6 haloalkynyloxy group include 3-fluoro-2-propynyloxy, 3-chloro-2-propynyloxy, 3-bromo-2-propynyloxy, 3-chloro-1-methyl-2-propynyloxy, 4,4,4-trifluoro-2-butynyloxy, 4-chloro-3-butynyloxy and 5-chloro-4-pentynyloxy; examples of the C3-C6 cycloalkoxy group include cyclopropoxy, cyclopentyloxy and cyclohexyloxy; examples of the C3-C6 cycloalkenyloxy group include cyclopentenyloxy and cyclohexenyloxy; examples of the cyano C1-C5 alkoxy group include cyanomethoxy, 1-cyanoethoxy and 2-cyanoethoxy; examples of the C1-C6 alkylthio group include methylthio, ethylthio, propylthio, butylthio, isobutylthio, sec-butylthio, pentylthio and hexylthio; examples of the C1-C6 haloalkylthio group include trifluoromethylthio, difluoromethylthio, bromodifluoromethylthio, chlorodifluoromethylthio, fluoromethylthio, 2,2,2-trifluoroethylthio and 1,1,2,2-tetrafluoroethylthio; examples of the (C1-C5 alkoxy)carbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl and pentyloxycarbonyl; examples of the optionally substituted phenoxy group include phenoxy, 4-chlorophenoxy, 4-methylphenoxy, 4-methoxyphenoxy and 4-trifluoromethylphenoxy; examples of the optionally substituted benzyloxy group include benzyloxy, 4-chlorobenzyloxy, 4-methylbenzyloxy, 4-methoxybenzyloxy and 4-trifluoromethylbenzyloxy; and examples of the C2-C6 alkylenedioxy group include ethylenedioxy, propylenedioxy and trimethylenedioxy. Among them, preferable are methoxy for Z1 and methoxy and 2-propynyloxy for Z2.
In the present compounds, there exist (E) and (Z) isomers based on Cxe2x95x90C double bond bonded with Ar and X, and the present invention include each isomer and mixtures thereof.
In the present compounds, the compounds having excellent efficacy for controlling plant diseases are exemplified by N-[2-(3,4-dimethoxyphenyl)ethyl]-3-difluoromethoxy-2-(4-methylphenyl)acrylamide, N-[2-(3,4-dimethoxyphenyl) ethyl]-3-difluoromethoxy-2-[2-(5,6,7,8-tetrahydronaphthalen-2-yl)acrylamide, N-[2-{3-methoxy-4-(2-propynyloxy)phenyl}ethyl]-3-difluoromethoxy-2-(5,6,7,8-tetrahydronaphthalen-2-yl)acrylamide, N-[2-{3-methoxy-4-(2-propynyloxy) phenyl}ethyl]-3-difluoromethoxy-2-(4-methylphenyl)acrylamide, N-[2-(3,4-dimethoxyphenyl)ethyl]-3-difluoromethoxy-2-(4-chlorophenyl)acrylamide and N-[2-{3-methoxy-4-(2-propynyloxy)phenyl}ethyl]-3-difluoromethoxy-2-(4-chlorophenyl)acrylamide.
The present compounds can be produced, for example, by the following [Production method A], [Production method B] or [Production method C]. In these production methods, a protective group may be utilized for protecting a functional group from chemical reaction, if necessary.
Production Method A
Production method of making the compound given by formula [II] to react with the compound given by formula [III]
In the above scheme, L1 represents a leaving group such as chlorine, bromine, iodine, p-toluenesulfonyloxy, methanesulfonyloxy and trifluoromethanesulfonyl; R11 represents C1-C10 haloalkyl group such as fluoromethyl, difluoromethyl, bromodifluoromethyl and fluoroethoxy, C3-C10 haloalkenyl group such as 3,3-dichloroally or C3-C10 haloalkynyl group such as 2-propynyl; and R2, X, Y, Ar, A, Z1 and Z2 have the same meanings as defined above.
Step 1 (process 1) in the above scheme is a process for producing the present compound given by formula [I-1] by making the compound given by formula [II] react with the compound given by formula [III] optionally in the presence of a base. The reaction temperature is usually in the range of 0-100xc2x0 C. and the reaction period is usually in the range of 1-24 hours. The amount of the compound given by formula [III] utilized for the reaction is usually 0.5-10 mols, preferably 1-3 mols based on 1 mol of the compound given by formula [II].
When the base is utilized for the reaction, the amount of the base is usually 1-10 mols moles based on 1 mol of the compound given by formula [II]. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride and the like; organic bases such as pyridine, triethylamine, ethyldiisopropylamine and the like; and mixtures thereof.
The reaction is usually carried out in a solvent. Examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as chlorobenzene; organic bases such as pyridine, triethylamine and N,N-dimethylaniline; esters such as butyl acetate and ethyl acetate; nitrites such as acetonitrile; N,N-dimethylformamide; dimethyl sulfoxide; water; and mixtures thereof.
The reaction solution after the reaction is subjected to usual work-up such as extraction with organic solvent, concentration and so on to provide the isolated objective product. The objective product can be purified by recrystallization, distillation, chromatography and so on.
The compound given by formula [I] wherein R1 is trifluoromethyl can be prepared according to the methods described in Tetrahydron Lett., 1973, 2253 and J. Org. Chem., 1979, 44, 3872. At that time, Production Example 15 given below can be comferred.
The compound given by formula [II] wherein X is oxygen and Y is also oxygen (the compound given by formula [II-1] in the scheme below) can be prepared according to the methods described in Chem. Ber., 1971, 104, 2709, J. Org. Chem., 1966, 61, 3358 and Adv. Heterocycl. Chem., 1981, 31, 207. It can be concretely produced according to the following scheme. 
In the above scheme, L3 and L4 are the same or different and represent alkoxy group such as t-butoxy group; L2 represents chlorine or bromine atom; and R2, Ar A, Z1 and Z2 have the same meanings as defined above.
The step 2-1 is a step of making the compound given by formula [IV] react with the compound given by formula [V] in the presence of a base to provide the compound given by formula [VI]. The reaction temperature is usually in the range of 0 to 100xc2x0 C. and the amount of the compound given by formula [V] is usually 1 to 5 mols based on 1 mol of the compound given by formula [IV].
The amount of the base used for the reaction is usually 1 to 10 mols based on 1 mol of the compound given by formula [IV]. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride; organic bases such as pyridine, triethylamine and ethyldiisopropylamine; and mixtures thereof.
The reaction is usually carried out in a solvent and examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as chlorobenzene; organic bases such as pyridine, triethylamine and N,N-dimethylaniline; esters such as butyl acetate and ethyl acetate; nitrites such as acetonitrile; N,N-dimethylformamide; dimethyl sulfoxide; water; and mixtures thereof.
The reaction solution after the reaction is subjected to usual work-up such as extraction with organic solvent, concentration and so on to provide the isolated objective product. The objective product can be purified by recrystallization, distillation, chromatography and so on.
The step 2-2 is a step of making the compound given by formula [VI] react with the compound given by formula [VII-1] or formula [VII-2] to provide the compound given by formula [VIII]. The reaction temperature is usually in the range of 50 to 150xc2x0 C., the reaction period is usually in the range of 1 to 24 hours and the amount of the compound given by formula [VII-1] or formula [VII-2] is usually 1 to 10 mols based on 1 mol of the compound given by formula [VI].
The reaction is usually carried out in a solvent and examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as chlorobenzene; organic bases such as pyridine, triethylamine and N,N-dimethylaniline; nitrites such as acetonitrile; N,N-dimethylformamide; dimethyl sulfoxide; and mixtures thereof.
The reaction solution after the reaction is subjected to usual work-up such as extraction with organic solvent, concentration and so on to provide the isolated objective product. The objective product can be purified by recrystallization, distillation, chromatography and so on.
The step 2-3 is a step of making the compound given by formula [VIII] react with excess water in the presence of an acid to provide the compound given by formula [II-1]. The reaction temperature is usually in the range of 0 to 100xc2x0 C. and examples of the acid include hydrochloric acid, sulfuric acid and p-toluenesulfonic acid. The amount of the acid is usually 0.1 to 100 mols based on 1 mol of the compound given by formula [VIII].
The reaction can be carried out in a solvent and examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as chlorobenzene; nitriles such as acetonitrile; N,N-dimethylformamide; dimethyl sulfoxide; and mixtures thereof.
The reaction solution after the reaction is subjected to usual work-up such as extraction with organic solvent, concentration and so on to provide the isolated objective product. The objective product can be purified by recrystallization, distillation, chromatography and so on.
Production Method B
Production method of making the compound given by formula [I-1] to react with 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (hereinafter, referred to as Lawesson""s Reagent) 
In the above scheme, R1, R2, X, Ar, A, Z1 and Z2 have the same meanings as defined above.
The step 3 is a step of making the compound given by formula [I-1] react with Lawesson""s Reagent in a solvent to provide the compound given by formula [I-2]. The reaction temperature is usually in the range of 50 to 150xc2x0 C. and the amount of the Lawesson""s Reagent is usually 1 to 10 mols based on 1 mol of the compound given by formula [I-1].
Examples of the solvent used for the reaction include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as chlorobenzene; organic bases such as pyridine, triethylamine and N,N-dimethylaniline; nitriles such as acetonitrile; N,N-dimethylformamide; dimethyl sulfoxide; and mixtures thereof.
The reaction solution after the reaction is subjected to usual work-up such as extraction with organic solvent, concentration and so on to provide the isolated objective product. The objective product can be purified by recrystallization, distillation, chromatography and so on.
Production Method C
Production method of making the compound given by formula [IX] to react with the compound given by formula [X]
In the above scheme, L5 represents p-toluenesulfonyl, methanesulfonyl or trifluoromethanesulfonyl, and R1, R2, Y, Ar, A, Z1 and Z2 have the same meanings as defined above.
The step 4 is a step of making the compound given by formula [IX] react with the compound given by formula [X]optionally in the presence of a base to provide the present compound given by formula [I]. The reaction temperature is usually in the range of 0 to 100xc2x0 C., the reaction period is usually in the range of 1 to 24 hours and the amount of the compound given by formula [X] is usually 0.5 to 10 mols, preferably 1 to 3 mols based on 1 mol of the compound given by formula [IX].
When the base is utilized in the above reaction, the amount of the base is usually 1 to 10 mols based on 1 mol of the compound given by formula [X]. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride; organic bases such as pyridine, triethylamine and ethyldiisopropylamine; and mixtures thereof.
The reaction is usually carried out in a solent and examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as chlorobenzene; organic bases such as pyridine, triethylamine and N,N-dimethylaniline; esters such as butyl acetate and ethyl acetate; nitriles such as acetonitrile; N,N-dimethylformamide; dimethyl sulfoxide; water; and mixtures thereof.
The reaction solution after the reaction is subjected to usual work-up such as extraction with organic solvent, concentration and so on to provide the isolated objective product. The objective product can be purified by recrystallization, distillation, chromatography and so on.
The compound given by formula [IX] can be, for example, produced according to the following scheme. 
In the above scheme, L5, R2, Ar, A, Z1 and Z2 have the same meanings as defined above.
The step 5 is a step of making the compound given by formula [II-1] react with the compound given by formula [X]optionally in the presence of a base to provide the present compound given by formula [IX]. The reaction temperature is usually in the range of xe2x88x9220 to 100xc2x0 C., the reaction period is usually in the range of 1 to 24 hours and the amount of the compound given by formula [XI] is usually 0.5 to 10 mols, preferably 1 to 3 mols based on 1 mol of the compound given by formula [IX].
When the base is utilized in the above reaction, the amount of the base is usually 1 to 10 mols based on 1 mol of the compound given by formula [II-1]. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride; organic bases such as pyridine, triethylamine and ethyldiisopropylamine; and mixtures thereof.
The reaction is usually carried out in a solent and examples of the solvent include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as chlorobenzene; organic bases such as pyridine, triethylamine and N,N-dimethylaniline; esters such as butyl acetate and ethyl acetate; nitriles such as acetonitrile; N,N-dimethylformamide; dimethyl sulfoxide; water; and mixtures thereof.
The reaction solution after the reaction is subjected to usual work-up such as extraction with organic solvent, concentration and so on to provide the isolated objective product. The objective product can be purified by recrystallization, distillation, chromatography and so on.
The compound given by formula [IV] can be, for example, produced according to the following scheme. 
wherein L2 and Ar mean as described above.
The compound given by formula [XII] can be produced according to the description in Syn. Commun., 1982, 21, 415, JP sho58-41862A, Tetrahedron Lett., 1980,21,2547, Syn. Commun., 1976, 6, 349 and J. Am. Chem. Soc., 1977, 99, 4833.
The compound given by formula [V] can be produced according to the description in Bull. Chem. Soc, Jpn., 1990, 63, 1252, J. Am. Chem. Soc., 1955, 77, 2544, Synthesis, 1975, 590 and Chem. Lett., 1984, 1733.
When the present compound is used as an active ingredient of fungicide, it can be used as it is without any other ingredient, but it is usually formulated to emulsifiable concentrates, wettable powders, water dispersible granules, emulsion formulations, flowables, dusts, granules and so on by mixing with solid carrier, liquid carrier, surfactant or the other auxiliaries and used. These formulations usually contain 0.1 to 90% by weight of the present compound.
Examples of the solid carrier utilized for the formulation include fine powders or granules of minerals such as kaolin clay, attapulgite clay, bentonite, montmorillonite, terra alba, pyrophilite, talc, diatomaceous earth and calcite; natural organic substances such as corncob and walnut shell; synthetic organic substances such as urea; salts such as calcium carbonate and ammonium sulfate; and synthetic inorganic substances such as synthetic hydrous silicon oxide. Examples of the liquid carrier include aromatic hydrocarbons such as xylene, alkylbenzene and methylnaphthalene; alcohols such as isopropanol, ethylene glycol, propylene glycol and cellosolve; ketones such as acetone, cyclohexanone and isophorone; vegetable oils such as soybean oil and cottonseed oil; paraffin type aliphatic hydrocarbons; esters; dimethyl sulfoxide; acetonitrile and water.
Examples of the surfactant include anionic surfactants such as alkylsulfate ester salts, alkylarylsulfonate salts, dialkyl sulfosaccinate salts, polyoxyethylenealkylary ether phosphate salts, ligninsulfonate salts and naphthalenesulfonate formaldehyde condensate; nonionic surfactants such as polyoxyethylenealkylary ether, polyoxyethylenealkylpolyoxypropylene block copolymers and sorbitan fatty acid esters.
Examples of the auxiliaries for formulation include water soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone; polysaccharides such as gum arabic, algin acid and its salts, CMC(carboxymethylcellulose) and xanthan gum; inorganic substances such as alminium magnesium silicate and almina sol; preservatives; coloring agent; PAP (isopropyl acid phosphate) and stabilizers such as BHT.
The application methods of the present compounds are typically foliar application and soil treatment.
When the present compound is used for controlling plant diseases, the dosage is usually 1 to 5000 g, preferably 5 to 1000 g per 1 hectare though it is variable depending on the type of plants (e.g. crops) to be treated, type of diseases to be controlled, degree of affection by the diseases, formulation type, application method, time of application, weather conditions and so on.
In case emulsifiable concentrates, wettable powders, flowables and the like are used as aqueous dilution, the concentration of the active ingredient is 0.0001 to 3% by weight, preferably 0.0005 to 1% by weight. Dusts, granules and the like are applied as they are without dilution. The present compound is also used for the other known application methods such as seed treatment. When it is used for seed treatment, seeds are usually soaked in 1 to 1000 ppm dilution of the present compound, or said dilution is sprayed to or daubed on the seeds. Further, dusts containing 0.1 to 10% by weight of the present compound may be applied by powder treatment.
The present compound can be used as agricultural/horticultural fungicide for controlling plant diseases in the plowed fields, paddy fields, orchards, tea plantations, pastures, lawns and the like. Also, an increased fungicidal effect can be expected by using the compounds in admixture with other fungicides. Examples of such admixable other fungicide include azole type fungicidal compounds such as propiconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromconazole, epoxyconazole, diphenoconazole, ciproconazole, metoconazole, triflumizole, tetraconazole, microbutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, bitertanol, imazalil and flutriafol; cyclic amine type fungicidal compounds such as fenpropimorph, tridemorph and fenpropidin; benzimidazole type fungicidal compounds such as carbendazim, benomyl, thiabendazole and thiophanate-methyl; procymidone; cyprodinil; pyrimethanil; diethofencarb; thiuram; fluazinam; mancozeb; iprodione; vinclozolin; chlorothalonil; captan; mepanipyrim; fenpiclonil; fludioxonil; dichlofluanide; folpet; kresoxim-methyl; azoxystrobin; trifloxystrobin; picoxystrobin; pyraclostrobin; N-methyl-xcex1-ethoxyimino-2-[(2,5-dimethylphenoxy) methyl]phenylactamide, spiroxamine; quinoxyfen; phenhexamid; famoxadone; fenamidon (RP-407213) and iprovalicarb.
The present compound can be used in combination with other agricultural/horticultural insecticides, acaricides, nematocides, herbicides, plant growth regulators and fertilizers. In the combination, they can be mixed in advance.
Examples of the insecticide, acaricide and nematocide include organophosphorus compounds such as fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl) phosphorothioate], fenthion [O,O-dimethyl O-(3-methyl-4-(methythio)phenyl) phosphorothioate], diazinon [O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate], chlorpyrifos [O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate], acephate [O,S-dimethyl acetylphosphoramidothioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl O,O-dimethyl phosphorodithioate], disulfoton [O,O-diethyl S-2-ethylthioethyl phosphorodithioate], DDVP [2,2-dichlorovinyl dimethyl phosphate], sulprofos [O-ethyl O-4-(methylthio)phenyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O,O-dimethyl phosphorothioate], dioxabenzofos [2-methoxy-4H-1,3,2-benzodioxaphosphorin 2-sulfide], dimethoate [O,O-dimethyl S-(N-methylcarbamoylmethyl) dithiophosphate], phenthoate [ethyl 2-dimethoxyphosphinothioylthio(phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate], azinphos-methyl [S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl O,O-dimethyl phosphorodithioate], monocrotophos [dimethyl (E)-1-methyl-2-(methylcarbamoyl) vinyl phosphate], ethion [O,O,Oxe2x80x2,Oxe2x80x2-tetraethyl S,Sxe2x80x2-methylene bis (phosphorodithioate)] and fosthiazate [N-(O-methyl-S-sec-butyl) phosphorylthiazolidin-2-one]; carbamate compounds such as BPMC [2-sec-butylphenyl methylcarbamate], benfracarb [ethyl N-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-isopropyl-xcex2-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo [b]furanyl N-dibuthylaminothio-N-methylcarbamate], carbaryl [1-naphthyl N-methylcarbamate], methomyl [S-methyl N-[(methylcarbamoyl)oxy]thioacetimidate], ethiofencarb [2-(ethylthiomethyl) phenyl methylcarbamate], aldicarb [2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime], oxamyl [N,N-dimethyl-2-methylcarbamoyloxyimino-2-(methylthio)acetamide] and fenothiocarb [S-4-phenoxybuthyl N,N-dimethylthiocarbamate]; pyrethroid compounds such as etofenprox [2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether], fenvalerate [(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate], esfenvalerate [(S)-xcex1-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate], fenpropathrin [(RS)-xcex1-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS)-xcex1-cyano-3-phenoxybenzyl (1RS, 3RS)-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(RS)-xcex1-cyano-3-phenoxybenzyl (Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S)-xcex1-cyano-m-phenoxybenzyl (1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethyl-cyclopropanecarboxylate], cycloprothrin [(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate], fluvalinate [xcex1-cyano-3-phenoxybenzyl N-(2-chloro-xcex1,xcex1,xcex1-trifluoro-p-tolyl)-D-valinate], bifenthrin [2-methylbiphenyl-3-ylmethyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethyl-cyclopropanecarboxylate]acrinathrin [cyano(3-phenoxyphenyl)methyl (1R-{1xcex1(S*), 3xcex1(Z)})-2,2-dimethyl-3-[3-oxo-3-(2,2,2-trifluoro-1-(trifluoromethyl)ethoxy-1-propenyl)cyclopropanecarboxylate], 2-methyl-2-(4-bromodifluoromethoxyphenyl) propyl 3-phenoxybenzyl ether, tralomethrin [(S)-xcex1-cyano-3-phenoxybenzyl (1R-cis) 3-(1,2,2,2-tetrabromoethyl)-2,2-dimethylcyclopropanecarboxylate], silafluofen [(4-ethoxyphenyl)(3-(4-fluoro-3-phenoxyphenyl)propyl) dimethylsilane]; thiadiazine derivatives such as buprofezin (2-t-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one); nitroimidazolidine derivatives; nereistoxin derivatives such as cartap (S,Sxe2x80x2-(2-dimethylaminotrimethylene)bis(thiocarbamate), thiocyclam [N,Nxe2x80x2-dimethyl-1,2,3-trithian-5-ylamine] and bensultap [S,Sxe2x80x2-2-dimethylaminotrimethylene di(benzenethiosulfonate)]; N-cyanoamidine derivatives such as N-cyano-Nxe2x80x2-methyl-Nxe2x80x2-(6-chloro-3-pyridylmethyl)acetamidine; chlorinated hydrocarbons such as endosulfan [6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine oxide], xcex3-BHC [1,2,3,4,5,6-hexachlorocyclohexane] and 1,1-bis(chlorophenyl)-2,2,2-trichloroethanol; benzoylphenylurea compounds such as chlorfluazuron [1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyn-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea], teflubenzuron [1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea] and flufenoxuron [1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea]; formamidine derivatives such as amitraz [N,Nxe2x80x2-[(methylimino)dimethylidine]di-2,4-xylidine] and chlordimeform [Nxe2x80x2-(4-chloro-2-methylphenyl)-N,N-dimethylmethanimidamide]; thiourea derivatives such as diafenthiuron [N-(2,6-diisopropyl-4-phenoxyphenyl)-Nxe2x80x2-t-butylcarbodiimide]; phenylpyrazole compounds; tebufenozide [N-t-butyl-Nxe2x80x2-(4-ethylbenzoyl)-3,5-dimethylbenzhydrazide]; 4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile; bromopropylate [isopropyl 4,4xe2x80x2-dibromobenzilate]; tetradifon [4-chlorophenyl 2,4,5-trichlorophenyl sulfone]; quinomethionate [S,S-6-methylquinoxalin-2,3-diyl dithiocarbonate]; propargite [2-(4-t-butylphenoxy)cyclohexyl prop-2-yl sulfite]; fenbutatin oxide [bis[tris (2-methyl-2-phenylpropyl)tin]oxide]; hexythiazox [(4RS, 5RS)-5-(4-chlorophenyl)-N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidin-3-carboxamide]; clofentezine [3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine]; pyridathioben [2-t-butyl-5-(4-t-butylbenzylthio)-4-chloropyridazin-3(2H)-one]; fenpyroximate [t-butyl (E)-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate]; tebufenpyrad [N-(4-t-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide]; polynactins complex [tetranactin, dinactin and trinactin]; milbemectin; abamectin; ivermectin; azadirachtin [AZAD]; pyrimidifen [5-chloro-N-[2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}ethyl]-6-ethylpyrimidin-4-amine] and pymetrozine [2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-3-yl)methyleneamino]-6-methyl-1,2,4-triazine.
Examples of the plant diseases to be controlled by the present compound include Pyricularia oryzae and Cochlioholus miyaheanus and Rhizoctonia solani of rice; Erysiphe graminis, Gibberella zeae, Puccinia striiformis, P. graminis, P. recondita, P. hordei, Typhula sp., Micronectriella nivalis, Ustilago tritici, U. nuda, Tilletia caries, Pseudocercosporella herpotrichoides, Rhynchosporium secalis, Septoria tritici and Leptosphaeria nodorum, of wheat and barley; Diaporthe citri, Elsinoe fawcetti, Penicillium digitatum and P. italicum of citrus; Sclerotinia mali, Valsa mali, Podosphaera leucotricha, Alternaria mali and Venturia inaequalis of apple; Venturia nashicola, V. pirina, Alternaria kikuchiana and Gymnosporangium haraeanum of pear; Sclerotinia cinerea, Cladosporium carpophilum and Phomopsis sp. of peach; Elsinoe ampelina, Glomerella cingulata, Uncinula necator, Phakopsora ampelopsidis, Guignardia bidwellii and Plasmopara viticola, of grape; Gloeosporium kaki, Cercospora kaki and Mycosphaerella nawae of Japanese persimmon; Colletotrichum lagenarium, Sphaerotheca fuliginea, Mycosphaerella melonis, Fusarium oxysporum, Pseudoperonospora cubensis and Phytophthora sp. of gourd; Alternaria solani, Cladosporium fulvum, Phytophthora infestans and Pythium sp. of tomato; Phomopsis vexans and Erysiphe cichoracearum, of eggplant; Alternaria japonica and Cercosporella brassicae of Cruciferae vegetables; Puccinia allii of leek; Cercospora kikuchii, Elsinoe glycines and Diaporthe phaseolorum var. sojae of soybean; Colletotrichum lindemthianum of kidney bean; Cercospora personata and Cercospora arachidicola of peanut; Erysiphe pisi of pea; Alternaria solani and Phytophthora infestans of potato; Sphaerotheca humuli of strawberry; Exobasidium reticulatum and Elsinoe leucospila of tea; Alternaria longipes, Erysiphe cichoracearum, Colletotrichum tabacum, Peronospora tabacina and Phytophthora nicotianae of tobacco; Cercospora beticola of sugar beet; Diplocarpon rosae and Sphaerotheca pannosa of rose; Septoria chrysanthemi-indici and Puccinia horiana of chrysanthemum; and Botrytis cinerea and Sclerotinia sclerotiorum of various crops.